JPH01503627A - Novel carbamates, their production and their use as fuel additives - Google Patents

Abstract

A process for the production of a carbamate having the formula: <CHEM> wherein X and Y are independently either hydrogen, a hydrocarbyl group or a hetero-substituted hydrocarbyl group or the group of formula: <CHEM> wherein Z is either a divalent hydrocarbyl, a substituted hydrocarbyl group or the group of formula: [ (alkylene)m(NH)n(alkylene)m ] (III) in which n = 0 to 4 and m = 1 to 4, and R is a hydrocarbyl or substituted hydrocarbyl group, provided that if either one of X or Y is the group of formula (II), the other of X or Y is hydrogen, which process comprises reacting a compound of the formula<EMI ID=00.3 HE=20 WI=125 TI=CF> wherein X and Y are independently either hydrogen, a hydrocarbyl group or a hetero-substituted hydrocarbyl group with a dihydrocarbyl carbonate having the formula: <CHEM> wherein independently R is as defined above in the presence as catalyst of a strong organic base and in the proportions necessary to produce either a mono-carbamate or a bis-carbamate.

Description

[Detailed description of the invention] Novel carbamates, their production and Its use as a fuel additive The present invention relates to novel carbamates, their preparation and their use as fuel additives. It is something to do.

Carbamates are useful in pesticides, resins, plasticizers and monomers. many cures Therapeutic uses include use as an antipyretic, diuretic and preservative. carbamate A widely used method for producing is alkyl isocyanates and alcohols. This is a reaction with Le. The disadvantage of this method is that alkyl isocyanates are highly toxic substances. It is to be. Other reported methods for producing carbamates include It is disclosed in Japanese Patent Application Laid-Open No. 77-14745, and here NaOMe/MeO H and 1) h N H2 and (MeO)2Go are reacted to form PilNH-C02 JP-A No. 79-163528@publication produces NaOMe, piperidine. imidazole, carbonyldiimidazole A similar reaction is disclosed in Zarani U.S. Pat. No. 4,258,683. An aromatic amine is reacted with an organic carbonate in the presence of zinc and stannous salts, and U.S. Pat. No. 4,268,684 discloses that a cobaltous salt is substituted for the zinc salt and the cobaltous salt. A reaction similar to that of US Pat. No. 4,268,683 is disclosed, except that .

Additionally, carbamates are also used as additives to fuels.

A particular problem that appears to be involved in deposit formation in the combustion chamber is increased octane demand ( (generally abbreviated as ORI). The problem with ORI is U.S. Patent No. 4,23 No. 6,020, the solution to the problem in this U.S. patent is soluble poly(oxyalkylene) carbamate in a hydrocarbon fuel boiling in It is added to fuel. Carbame of U.S. Patent No. 4,236,020 is at least 5 carbon atoms having 2 to 5 carbon atoms per oxyalkylene unit. Hydrocarbyloxy-terminated poly(oxyalkylene) having oxyalkylene units xylene) chains, and these oxyalkylene units are linked via an oxycarbonyl group. and is bonded to the nitrogen atom of ethylenediamine. The preferred carbamate has the general formula : [wherein, 9 is an integer of 2 to 5, and j is the molecular weight of the compound of about i, 200 to is an integer in the range of approximately s, ooo, and Z has 1 to 30 carbon atoms. A hydrocarbyl having an oxyalkylene monomer in a compound other than ethylene. levels are sufficient to make these compounds soluble in hydrocarbon fuels boiling in the gun range. ] This is shown by The only method disclosed for producing carbamates is cleared by reaction of a suitable capped polyether alcohol with phosgene. chloroformate is formed and the chloroformate is then combined with ethylenediamine. This method produces active carbamates through the reaction of How to reach carbamate The problem with this method is the use of phosgene, which is highly toxic. as well as chlorine-contaminated products.

This time, we have discovered an improved method for producing carbamates using a strong organic base as a catalyst. .

Therefore, in a first aspect, the invention provides the formula: % formula %() [In the formula, Xa5 and Y are independently hydrogen, a hydrocarbyl group, or a heterosubstituted a divalent hydrocarbyl group or a group of formula: where Z is a divalent hydrocarbyl group; or substituted hydrocarbyl group or formula: %formula%() is a group of formula (I[I), where n=O~4 and m=1~4, and Furthermore, R is hydrocarbyl or a substituted drocarbyl group, with the proviso that X or If either one of Y is a group of formula (II), the other of X or Y is hydrogen] When producing a carbamate with the formula: % formula %) [wherein X and Y are independently hydrogen, hydrocarbyl or heterosubstituted is a hydrocarbyl group] in the presence of a strong organic base as a catalyst. dihydrocarbyl carbonate having the formula: [wherein R independently has the above meaning] to form either a mono-carbamate or a bis-carbamate. A method for producing a carbamate, characterized by carrying out the reaction at the ratio required to produce a carbamate. I will provide a.

Preferably, per mole of dihydrocarbyl carbonate of formula (V) at least 1 mol of compound of formula (IV) is used.

The compound of formula (1v) has ammonia (X=Y-H), a primary amine (x and Y (either X or Y is H) or a secondary amine (neither X or Y is H) can be done. The amine is preferably either a monoamine or a polyamine. You can. X and Y are independently a hydrocarbyl group or a heterosubstituted hydrogen group. It may be any drocarbyl group.

Preferably, the hydrocarbyl group is an aliphatic hydrocarbyl group, of which an alkyl Kill groups are preferred. Examples of suitable hydrocarbyl groups are methyl, ethyl, propyl Or it includes a butyl group. Alternatively, X and Y are independently heterosubstituted It may also be a hydrocarbyl group. Preferably, heterosubstituted hydrocarbyl The group can be an aliphatic hydrocarbyl group substituted by nitrogen or oxygen. and preferably the formula -P-Q [wherein P is an alkylene or polyalkylene group] , for example, a 01-C4 alkylene group or a poly01-C4 alkylene group. Q is NH2, -OH or a heterocyclic group, such as morpholine or piperidine. or a substituted heterocyclic group such as pipecoline. X and of suitable compounds (IV) in which Y is independently a heterosubstituted hydrocarbyl group; Examples are alkanolamines such as ethanolamine, as well as those of formula (IV). hand (i) Compounds that are X-H and Y-CH2Cl-12NH2 are included. lastly , X and Y are independently heterosubstituted hydrocarbyl groups (IV ) can be an alkylene polyamine or a polyalkylene polyamine, Preferably, the alkylene group is a 01-C4 alkylene group, such as ethylene. Can be used as diamine, diethylenetriamine, triethylenetetramine, etc. Wear.

In the dihydrocarbyl carbonate of formula (V), the group R independently represents a hydrocarbyl carbonate. A rubyl group, preferably an alkyl group, preferably a C1-C4 alkyl group, Preferably, it can be a methyl group. Alternatively, dihydrocargol of formula (V) Carbonates are cyclic carbonates, such as ethylene carbonate or plastics. It can be lopylene carbonate.

The process can be operated in the presence or absence of entrained solvents. suitable solution The agent is a liquid hydrocarbon solvent, such as those commercially available from BP Chemicals Ltd. A mixed aromatic solvent called A260.

The catalyst is a strong organic base. A preferred strong organic base is amidine. It's called amidine The term is the formula: [In the formula, the free valence on the nitrogen atom is bonded to either a carbon atom or a hydrogen atom.] , and the free valence on the carbon atom is bound to either another carbon atom or nitrogen. means a compound having a group of Free valences in nitrogen bond to nitrogen , then amidine is guanidine.

A preferred class of amidines are cyclic amidines. Cyclic amidines have a small number of nitrogen atoms. at least one alicyclic or heterocyclic substituted or unsubstituted hydrocarbyl ring Defined as amidines that are part of the Amidine is guanidine In this case, the two or three nitrogen atoms can be located in the same or different rings. Wear. Nitrogen atoms that are not part of the ring may be substituted or unsubstituted hydrocarbyl atoms. It can form part of a group.

Preferred types of cyclic amidines include those in which the amidine group is a 6-membered ring and a 5-membered ring or a 6-membered ring or a 6-membered ring. and those that can constitute part of a fused ring system having a 7-membered ring or two 6-membered rings. and for example 1,5-diazabicyclo[4,3,0]non-5-ethyl (DBN), or formula: 1,8-diazabicyclo[5,4,01 undec-7-enine (TBD) Ru.

The amidine can be supported on a suitable support. This is the amidine on the support. or by chemically bonding the amidine to a suitable support. Wear. Suitable supported amidine catalysts are, for example, those described in European patents by the applicant. It is described in patent application No. 0168167@.

As an alternative to amidines, strong bases consist of Lewis bases and epoxides You can also do that. The term Lewis base generally refers to a lone pair of electrons that can be shared with an acid. is understood to mean a compound having The terms Lewis base and amidine are therefore not mutually exclusive. The Lewis base is preferably trivalent nitrogen or phosphorus. eg an amine or a phosphine.

The epoxide is preferably substituted or unsubstituted 02-C8 alkylene oxide, preferably or ethylene oxide, propylene oxide or butylene oxide. Can be done.

Regarding the reaction conditions, this method is preferably conducted at temperatures between 0 and 100°C, more preferably between 15 and 75°C. ℃, particularly preferably in the range from 20 to 25 ℃, and the pressure is high. It can be at atmospheric pressure or overpressure, for example from 1 to 10 bar.

The process can be operated batchwise or continuously, preferably continuously.

An advantage of using the method of the invention to produce carbamates is the use of phosgene and The aim is to avoid this and its accompanying drawbacks.

The group R in the carbamate of formula (I>) can also be replaced by a group R1, and the method is a strong organic base or titanate tetrahydride using a carbamate of formula (I> as a catalyst) Formula in the presence of local building: %formula%() [wherein R1 is a hydrocarbyl group different from R or a heterosubstituted hydrocarbyl group] Co., which is a building base It consists of reacting with a compound of

The group R1 in the compound of formula (VI) is preferably defined for the carbamate of formula (1). can be any of the radicals R as defined above, provided that it is not identical to the radical R. shall be. Hydrocarbyl groups substituted with nitrogen and/or oxygen, e.g. Locarbyl polyether groups can be used.

In a preferred embodiment of the invention, it is used as a detergent additive to internal combustion engine fuel. A method for preparing carbamates suitable for use is provided, wherein a compound of formula (Vl) The group R1 in the compound has, for example, a molecular weight and composition that confers fuel solubility. or a heterosubstituted hydrocarbyl group.

Compounds of formula (VI>) suitable for this purpose are alcohols or phenols. The polymer produced by the reaction of alkylene oxide with a hydroxyl compound that can be realkylene glycol (PAG), preferably about 500 to io, ooo, More preferably, it can have a molecular weight in the range of 1,200 to 5,000. .

PAG is described in more detail in the aforementioned U.S. Pat. No. 4,236,010. , the disclosure of which is hereby incorporated by reference with respect to the appropriate PAG. P.A.G. Contains sufficient oxyalkylene units other than ethyleneoxy to be used as an internal combustion engine fuel. The solubility must be at least 60%. Particularly suitable for use in the method of the invention The compound of formula (Vl) is obtained by the reaction of p-dodecylphenol and butylene oxide. commercially available polyoxyalkylene glycol with a molecular weight of about 2,000. This substance is available as PREOX (registered trademark) from Hite Chemicals Limited. > Commercially available as PCl362. For use in manufacturing detergent additives Other suitable classes of compounds of formula (Vl) can be prepared by hydroxyalkylation. Preferably alkylene oxides and amines, such as ethylene diamine or aminopropylene. It is a polyalkylene glycol produced by reaction with lopylmorpholine.

Tetrahydrocarbyl titanate is used as a catalyst for exchange reactions up to strong organic bases. Either file is used. Suitable strong organic bases are suitable for the preparation of carbamates of formula (1). The structure is the same as described above. Same strong organic base or different strong organic base , preferably the same, in the exchange reaction as in the preparation of carbamates of formula (I>). It can be used accordingly. Preferably, tetrahydrocarbyl titanate can do. Preferably, the alkyl group of the tetraalkyl titanate is C1- It can be a C4 alkyl group. An example of a suitable tetraalkyl titanate is titanate. Tetraisopropyl phosphate.

Reacting a compound of formula (I) with a compound of formula (Vl) in the presence of a suitable solvent suitable. Preferably, the solvent may be a hydrocarbon solvent, such as BPK. Mixed aroma identified as A260 commercially available from Michals Ltd. It is a group hydrocarbon solvent.

Regarding the reaction conditions for reacting the compound of formula (1) with the compound of formula (Vl), , the temperature can be increased preferably to a range of 100-300°C, and the pressure can be increased It can be at atmospheric pressure or overpressure.

A particular advantage of the process according to the invention for producing detergent additives is, for example, In contrast to prior art methods such as Patent No. 4,236,020, chlorine-free of the product.

Other aspects. The present invention also provides a concentrated composition of internal combustion engine fuel, which composition The substance has the formula (■) in the amount of 1 to 95% by weight as the first component [in the formula, the group R imparts fuel solubility] Hydrocarbyl or substituted hydrocarbyl having a molecular weight and composition such that a carbamate such as that produced by the above-mentioned method with a group of and a fuel-compatible solvent.

The fuel compatible solvent for the compound of formula (I) is preferably an internal combustion engine fuel. I can do it.

Preferably the carbamate is a monocarbamate.

In one aspect, the present invention provides an internal combustion engine fuel composition, which composition The concentration of the compound of formula (I) in the internal combustion engine fuel and a small proportion of said fuel composition The amount can be such that the concentration ranges from 10 to 10,000 ppm by weight.

Preferably, the internal combustion engine fuel is a fuel boiling in the gasoline range. fuel composition The materials can be incorporated with additives conventionally used in fuel compositions.

Additives of this type can be incorporated into fuel concentrates or directly into fuel compositions. .

In another aspect, the present invention provides novel compounds as disclosed in U.S. Pat. No. 4,236,0 Carbamates of the formula (I> other than those disclosed in Publication No. 20, especially where X and Y are independently a group of the formula -P-Q, and preferably R1 has a fuel solubility Hydrocarbyl groups or heterosubstituted The reaction product with a compound of formula (H), which is a hydrocarbyl group, is provided.

Hereinafter, the present invention will be briefly explained with reference to Examples.

Dimethyl carbonate (9.0 g) and n-butylamine (7.3 g) are BD (mixed with 0.05 (l) and allowed to stand at air temperature. After 6 hours, the liquid A sample of the product is methyl N-(n-butyl)carbamate by gc/ms (95% yield).

X fish plate-2 Dimethyl carbonate (9.09> and n-propylamine (5.9 (J) and TBD (0.05()) were mixed according to Example 1. The product was g c/ms showed that it was methyl N-(n-propyl)carbamate. 93% yield).

X Thoughts and Yu Dimethyl carbonate (9.0g> and ethanolamine (4.7g>) in TBD (0,05q) and Example]. This product is gc7ms It was shown to be methyl N-(2-hydroxylethyl)carbamate. (86% yield).

X medicine series-A was shown to be ethyl N-(n-butyl)carbamate by gc7ms. (92% yield).

Comparative test 1 Example 1 was repeated in the absence of TBD. Only starting material was recovered.

Technical School Star Violet Example 1 was repeated using triethylamine (0.05 g) instead of TBD.

This liquid product was determined by gc/ms as methyl N-(n-butyl)carbamate. (6% yield).

Example 5 Example 1 was repeated using DBU in place of TBD. This liquid product is gc/ ms shows that it is methyl N-(n-butyl)carbamate65 %yield).

Example 6 Example 1 was repeated using DBN instead of TBD. This liquid product is gc/m It was shown to be methyl N-(n-butyl)carbamate by s (30% yield).

Example 7 Ethanolamine (50,6(1) and dimethyl carbonate (74,8()) A mixture of TBD (1,0 g) and m-xylene (1(7)) was refluxed for 3 hours. (approximately 80°C). The mixture was evaporated under reduced pressure to give the product as a clear liquid. (84g). NMR analysis shows that the product is N-(2-hydroxylethyl)cal. It was shown to be methyl bamate.

Example 8 N-(2-aminoethyl)piperazine (28Q) and dimethyl carbonate (2 0g> and TBD (1,0g>) for 120 hours while exposing it to the atmosphere. or let it stand still. The mixture was evaporated under reduced pressure and NMR determined that N-[2-( The product identified as methyl N1-piperazino)ethyl]carbamate (3 8.75 (11) was obtained.

Example 9 N-(3-aminopropyl)pipecoline (37.1g) and dimethyl carbonate A mixture of TBD (23,0g) and TBD (1,00) was exposed to the atmosphere while It was left to stand for 20 hours. The mixture was evaporated under reduced pressure and NMR determined that N-[3 -(N1-pipecoline)ethyl]product identified as methyl carbamate (46,19) was obtained.

X Okitara-Yuoi: N-(3-aminopropyl)morpholine (57, IQ) and dimethyl carbonate A mixture of TBD (420) and TBD (1.0 g) was heated for 6 hours while being sparged with nitrogen. Refluxed. The resulting mixture was evaporated under reduced pressure to convert the product into a clear yellow liquid (74 g>. NMR analysis shows that the product is N-[3-(N1-morpholino) It was shown to be methyl probilcocarbamate.

Process (B) Intermediate carbamate (16,5(]) from step (A>) and preox P C1 362 (114g) and TBD (1.0g>) at 150°C for 3.5 hours. The mixture was stirred under a nitrogen sparge. The mixture was cooled and toluene (50d> and magnesium sulfate (1.0 g) and allowed to stand. Then filter the mixture. Filtration and evaporation under reduced pressure gave the product as a clear pale yellow liquid.

Analysis: Actual nitrogen % = 1.46 N-(2-aminoethyl)piperazine (20q) and dimethyl carbonate (3 A mixture of 3,6(1) and DBU(0,2(1) was heated to 80% by nitrogen sparge. Stirred at ~120°C for 2 hours. The mixture is cooled and filtered to remove the product. A clear orange-yellow liquid was obtained. NMR analysis revealed that this formation and N-[2-(Nl-pipe radino)ethyl] methyl carbamate.

Process (B) Intermediate carbamate product from step (A) [DBU catalyst carried over from step (A>)] 10,8Cl containing medium] and Preox P C1362 (136(]) The mixture was stirred at 120 to 140°C for 3 hours under a nitrogen sparge. cool the product and filtered to obtain a clear yellow liquid.

Analysis: Nitrogen % = 1.10.

Example 12 Methyl N-[3-(N1-morpholino)propyl]carbamate [Example 10] Step (intermediate product obtained from A>) (10 (II) and 1-octatool (1 5,00), m-xylene (25mi> and TBD (0,2Q>). It was refluxed for 1 hour.

The mixture was evaporated under reduced pressure to give the product as a pale yellow liquid (30.4g). . NMR analysis shows that the product is N-[3-(N1-morpholino)propylcocarboxylic. It was shown to be vamine in-octyl.

Example 13 Methyl N-[3-(Nl-morpholino)brobylcocarbamate [Example 10] Intermediate product co(5,2+;l) obtained from step (A>) and polyalkylene glycerin Cole [PAG 8225 from Hite Chemicals Limited] (49 ,50> and TBD (a mixture of 0,4(1> and m-xylene (33,49) The mixture was stirred at 140° C. for 2 hours while being sparged with nitrogen. Evaporate this mixture under reduced pressure The product was obtained as a viscous yellow liquid (45(1)).

Daijuku-Yu A Methyl N-[2-(N1-piperazino)ethyl]carbamate [Production of Example 8] material] (5,h), 1-octatool (4,3a), and TBD (0,6g ) was heated at 150°C for 2 hours. This mixture was evaporated under reduced pressure. , a reddish-brown product (8,2(]) was obtained, which was determined by NMR analysis to be N-[2 -(N1-piperazino)ethyl]carbamine ln-octyl Ta.

X Dust - Yu Branch Methyl N-[3-(N1-morpholino)propyl]carbamate [Example 10] Intermediate product obtained from step A] (16,0(1) and preox PCl470 [Manufactured by Hite Chemicals Limited, p-dodecylphenol] (1 mol) and butylene oxide (15 mol)] (10 , 35 (1) and TBD (0,90>) while sparging with nitrogen. Stirred at ℃ for 4.25 hours. The mixture was then cooled and toluene (50d) and magnesium sulfate (1,0Q) and allowed to stand. Then the mixture Evaporation under reduced pressure gave a clear liquid product.

Analysis: Nitrogen% = 1.55° Production of carbamate of formula (I) Example 16 Dimethyl carbonate (ia, og) and bis(3-aminopropyl)amine ( 13,1! ;] ) and mixed with TBD (0,05c+) in a round bottom flask, And it was allowed to stand still at air temperature. After 16 hours, the contents of the flask solidify and this solid is Recrystallization from toluene gave 16.90 white needle crystals (yield 96%).

mpios~107°C. H' and C1C13N matched structure (1).

Example 17 Dimethyl carbonate (25m! Rito bis(aminopropyl)amine (25mf) and TBD (0.1 g) were added. There was a slight heat generation. Accepted, the mixture was allowed to stand for 16 hours. The mixture is then passed through a rotary evaporator. Stripped and the solid residue was recrystallized from toluene. The product is , is bis[methyl(N-propyl)carbamate]amine by NMR. It has been shown.

Add ethylenediamine (6g) and dimethyl carbonate (18q) to a round bottom flask. The mixture was mixed in a tank at 20°C. Add TBD (0,1(]) and mix It was allowed to stand for 24 hours. After this time, collect the white solid product and bis(methoxycarbonyl) by recrystallization from Bis(methoxycarbonyl)ethylenediamine (iy ．． ag) and Preox (registered trademark>PC1362 (412(!>[High Te Chemicals Limited] and A260 [BP Chemicals Limited] (0.52) and heated vigorously to 160°C. Heat in the presence of titanate/tetraisopropyl (5 g) for 24 hours while stirring. did. A continuous stream of dry nitrogen was passed over the reactants.

The resulting pale yellow liquid was cooled and filtered through sintered glass. Nitrogen content is 0. It was measured to be 25%.

Example 19 Use PAG B 225 (360q> instead of Preox P C 1362) The procedure of Example 18 was repeated.

The nitrogen content of the product was determined to be 0.37%.

X-plate Use PAG B 335 (480Q) instead of Preox P C 1362 The procedure of Example 18 was repeated.

The nitrogen content of the product was determined to be 0.16%.

engine test X Naomasu - Mata Yuji 24 The products of Examples 10, 11, 18 and 19 were added to Opel Kadeck at various concentrations. It was evaluated using a gasoline detergent property test.

This Ober Cadet Gasoline Detergent Properties Test Reference No. by Lopian Kancil (C.E.C.). c. E. C. F. -02-T-79 is a well-known industrially approved evaluation method.

Concentrations and test results are shown in the table below.

Comparative test 3 0.0 in place of the biscarbamate products of Examples 10, 11, 18 and 19. 7 The procedures of Examples 21-24 were carried out using a commercial gasoline detergent with a nitrogen content of 0%. The sequence was repeated.

The test results are shown in the table below.

*Numbers in parentheses are base fuel.

As can be seen from the results shown in the table, the products of Examples 10 and 11 are commercially available products. Comparatively, the products of Examples 18 and 19 are suitable as detergents; Has activity.

Leap II! ! II Trial Scale Cow +m5m5+nea-^os++allll111@, pcfu, /Gyo a8 /CO494

Claims (31)

[Claims] 1. formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X and Y are independently hydrogen, Hydrocarbyl group or heterosubstituted hydrocarbyl group or formula: ▲ Formula , chemical formulas, tables, etc. ▼ is the group of (II), and in formula (II), Z is a divalent Hydrocarbyl or substituted hydrocarbyl group or formula: [(alkylene)m (NH)n(alkylene)m](III), and in formula (III), n = 0 to 4 and m = 1 to 4, and R is hydrocarbyl or substituted a hydrocarbyl group, provided that either X or Y is a group of formula (II) If so, the other of X or Y is hydrogen] When producing a carbamate with a formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(IV) [In the formula, X and Y are independently hydrogen, a hydrocarbyl group, or a hetero a substituted hydrocarbyl group] in the presence of a strong organic base as a catalyst. Under the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) [In the formula, independently, R is the above dihydrocarbyl carbonate having the meaning of ] and mono-carbamate in the proportions required to produce either bis-carbamate or bis-carbamate. A method for producing carbamate, which comprises reacting. 2. Whether the compound of formula (IV) is ammonia, a primary amine or a secondary amine The method according to claim 1, wherein: 3. Claims that the compound of formula (IV) is either a monoamine or a polyamine The method according to item 2 of the scope of the invention. 4. X and Y in formula (IV) are aliphatic hydrocarbyl groups, which are The method according to claim 2 or 3, wherein the method is an alkyl group. 5. a hydrocarbyl in which X and Y in formula (IV) are independently heterosubstituted; group, which is an aliphatic hydrocarbyl group substituted by nitrogen or oxygen The method according to claim 2 or 3. 6. A heterosubstituted hydrocarbyl group has the formula -P-Q [wherein P is an alkylene group] and Q is either NH2, OH or a heterocyclic group] The method according to claim 5. 7. In the dihydrocarbyl carbonate of formula (V), the group R is independently C1- 7. The method according to any one of claims 1 to 6, wherein the C4 alkyl group is a C4 alkyl group. 8. Claims 1 to 7, wherein the catalyst is a strong organic base, which is amidine. The method described in any one of paragraphs. 9. 9. The method of claim 8, wherein the amidine is a cyclic amidine. 10. Claims in which the catalyst is a strong organic base consisting of a Lewis base and an epoxide The method according to any one of items 1 to 7. 11. The compound of formula (IV) is heated at a temperature in the range 0 to 100°C and in the range 1 to 10 bar. Claims: reacting with a dihydrocarbyl carbonate of formula (V) at a pressure of The method according to any one of items 1 to 10. 12. The group R in the carbamate of formula (I) is replaced by a group R1, and the process is as follows: I) carbamate as a catalyst with a strong organic base or tetrahydrocar titanate Formula in the presence of Bill: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) [In the formula, R1 is a hydrocarbon different from R. is a hydrocarbyl group or a heterosubstituted hydrocarbyl group]. 12. A method according to any one of claims 1 to 11, comprising: 13. Molecular weight such that the group R1 in the compound of formula (VI) confers fuel solubility and a hydrocarbyl group or a heterosubstituted hydrocarbyl group of the composition and the product is a detergent additive to internal combustion engine fuel. Method described. 14. The compound of formula (VI) is reacted with a hydroxyl compound and an alkylene oxide. The method according to claim 13, wherein the polyalkylene glycol is produced from . 15. The polyalkylene glycol has a molecular weight in the range of about 500 to 10,000. 15. The method according to claim 14. 16. The compound of formula (VI) is reacted with P-dodecylphenol and butylene oxide. A polyalkylene glycol obtained by having a molecular weight of about 2,000 14. The method according to claim 13. 17. Compounds of formula (VI) were produced by hydroxyalkylation of amines. 14. The method according to claim 13, wherein the polyalkylene glycol is a polyalkylene glycol. 18. Provided that the catalyst is the same strong organic base used in the process for preparing the compound of formula (I). The method according to any one of claims 12 to 17. 19. The catalyst is tetrahydrocarbyl titanate, which is a tetrahydrocarbyl titanate. 18. The method according to any one of claims 12 to 17, wherein the method is Rukyl. 20. A compound of formula (I) is converted into a compound of formula (VI) in the presence of a solvent which is a hydrocarbon solvent. The method according to any one of claims 12 to 19, wherein the method is reacted with a compound. 21. The compound of formula (I) is heated at a temperature in the range of 100 to 300°C and at atmospheric pressure or Any of claims 12 to 20, wherein the compound is reacted with a compound of formula (VI) under pressure. The method described in paragraph (1). 22. Any one of claims 13 to 21 in which the first component is 1 to 95% by weight. a carbamate of formula (I) produced by the method described in item 1; and a fuel-compatible solvent. 23. 23. The concentrated composition of claim 22, wherein the solvent is an internal combustion engine fuel. 24. Claims 22 and 30, wherein the carbamate of formula (I) is a monocarbamate. or the concentrated composition according to item 23. 25. A large proportion of internal combustion engine fuel and a small proportion of the concentrated fuel according to claim 22 An internal combustion engine fuel composition comprising: 26. The amount of concentrated composition ranges from 10 to 10,000 ppm (by weight) in the final composition. Claim 25 is such that the concentration of the compound of formula (I) in Compositions as described. 27. Claim 2, wherein the internal combustion engine fuel is a fuel boiling in the gasoline range. The composition according to item 5 or item 26. 28. Formula (I) other than those described in U.S. Pat. No. 4,236,020 Bamate. 29. X and Y are independently of the formula -P-Q [wherein P is alkylene or polyamine] alkylene group, and Q is either -NH2, -OH or a heterocyclic group. A carbamate of formula (I) which is a group of 30. A carbamate according to claim 29, wherein Q is a heterocyclic group. 31. R=R1, which is the molecular weight and composition that confers fuel solubility. or a heterosubstituted hydrocarbyl group having A carbamate of formula (I) according to item 30.